Electrocatalytic hydrodeoxygenation of guaiacol on Pt/TiO2: The modulation on guaiacol adsorption and H spillover

doi:10.1016/S1872-2067(26)65133-9

Abstract

Abstract:

The synthesis of KA oil (a cyclohexanone-cyclohexanol mixture) from guaiacol through mild electrocatalytic approach represents a sustainable strategy for biomass valorization. Herein, we report the electrocatalytic conversion of guaiacol to KA oil over the reduced Pt/TiO₂ catalysts. The TiO₂-induced hydrogen spillover effect facilitates strategic modulation of H_ads(H*) coverage on Pt surfaces, thereby effectively suppressing competitive aromatic ring hydrogenation and excessive hydrogen evolution reactions. Comparative studies of electrocatalysis and thermocatalysis have demonstrated that Pt active sites serve as the dominant catalytic centers. However, H spillover significantly influences reactivity and selectivity, particularly in the electrocatalytic pathways. The electrocatalytic system demonstrates preferential C-O bond cleavage with KA oil selectivity around 70%. This work provides valuable insights into the regulation of metal-support interactions in the design of electrocatalysts.

Key words: Electrocatalytic hydrodeoxygenation, Biomass, Pt nanoparticles, C-O cleavage, H spillover

Yiwei Zhao, Zuhang Jin, Cheng Tao, Rui Du, Yongzheng Shi, Chao Zhang. Electrocatalytic hydrodeoxygenation of guaiacol on Pt/TiO₂: The modulation on guaiacol adsorption and H spillover[J]. Chinese Journal of Catalysis, 2026, 88: 393-407.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65133-9

https://www.cjcatal.com/EN/Y2026/V88/I9/393

Figures/Tables 11

Fig. 1. (a) Conversion and selectivity of the Pt/TiO2 catalysts. (b) TOF of the Pt/TiO2 catalysts. (c) Product selectivity and GUA conversion rate (10 mmol L-1) over the Pt/TiO2-400R catalyst at different current densities. (d) The FE of products on Pt/TiO2-400R catalyst at different current densities. Reaction conditions: 1.0 mg catalyst, 10 mmol L-1 GUA, 10 mL 0.2 mol L-1 HClO4, -20 mA cm-2, 50 °C, 2 h.

Fig. 2. TEM images of Pt/TiO2-200R (a), Pt/TiO2-400R (b), Pt/TiO2-600R (c), Pt/SiO2-200R (d), Pt/SiO2-400R (e), Pt/SiO2-600R (f), Pt/C-200R (g), Pt/C-400R (h), and Pt/C-600R (i) catalysts.

Fig. 3. (a) XRD patterns of Pt/TiO2 catalysts calcined at 400 °C in air followed by subsequent hydrogen reduction at temperatures of 200, 400, and 600 °C. XPS spectra of Pt 4f (b), O 1s (c), and Ti 2p (d) for Pt/TiO2-200R, Pt/TiO2-400R, and Pt/TiO2-600R.

Fig. 4. Nyquist plots (a) and OCP curves (b) of Pt/TiO2-200R, Pt/TiO2-400R, and Pt/TiO2-600R. (c) LSV curves of Pt/TiO2-400R in the presence and absence of 10 mmol L-1 GUA. (d) Tafel slopes derived from polarization data for Pt/TiO2-400R. Reaction conditions: 1.0 mg of catalyst, 10 mmol L-1 of GUA, 10.0 mL of 0.2 mol L-1 HClO4, 50 °C.

Fig. 5. (a) H2-TPD profiles of Pt/TiO2 catalysts reduced at different temperatures. (b) H2-TPD profiles of the Pt-based catalysts on different supports.

Fig. 6. In-situ FTIR spectra of GUA on Pt/TiO2-200R (a), Pt/TiO2-400R (b), and Pt/TiO2-600R (c) catalysts. (d) Adsorption spectra of GUA on Pt/TiO2-200R (black), Pt/TiO2-400R (red), Pt/TiO2-600R (blue) after 180 min.

Fig. 7. Comparative GUA HDO over Pt/TiO2 catalysts. (a) Product selectivity and GUA conversion for Pt/TiO2-400R under electrocatalytic (solid cylinders) vs. thermocatalytic (hollow cylinders) conditions. (b) Product selectivity and GUA conversion over Pt/TiO2 catalysts reduced at 200-600 °C under electrocatalytic (solid cylinders) and thermocatalytic (hollow cylinders) regimes. Reaction conditions: 50 °C, 2 h, HClO4 or H2SO4 solution of equivalent pH. Electrocatalysis: 1 mg catalyst, 10 mmol L-1 GUA, 10 mL 0.2 mol L-1 HClO4, -20 mA cm-2. Thermocatalysis: 2.0 mg catalyst, 20 mmol L-1 GUA, 1 MPa 20% H2/Ar, 10 mL 0.2 mol L-1 HClO4.

Fig. 8. Possible reaction mechanism for the electrocatalytic HDO of GUA on Pt/TiO2-400R.

Table 4 Calculated adsorption configurations and energetics of hydrogen species on Pt/TiO2(101) and oxygen-deficient Pt/TiO2(101)-Ov surfaces. Blue, gray, red, and pink spheres represent Pt, Ti, O, and H atoms, respectively.

System	Item	ΔE (eV)	ΔE (KJ mol^-1)
Pt/TiO₂(101)	Slad-H1*	2.22	2114.42
Pt/TiO₂(101)	Slad-H2*	2.22	2114.42
Pt/TiO₂(101)-O_v	Slad-H1*	2.17	210.33
Pt/TiO₂(101)-O_v	Slad-H2*	2.17	210.33

Fig. 9. (a) Stability assessment of the Pt/TiO2-400R catalyst via five consecutive GUA conversion cycles under a constant current density of -20 mA cm-2. (b) LSV curves of Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs in 0.2 mol L-1 HClO4 electrolyte containing 10 mmol L-1 GUA. (c) XRD patterns of Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs. (d) TEM images of used-Pt/TiO2-400R-5 runs. Reaction conditions: 1.0 mg of catalyst, 10 mmol L-1 of GUA, 10.0 mL of 0.2 mol L-1 HClO4, -20 mA cm-2, 50 °C, 2 h.

Fig. 10. (a) H2-TPD profiles of Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs. XPS spectra of Ti 2p (b), O 1s (c), and Pt 4f (d) for fresh Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs.

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Electrocatalytic hydrodeoxygenation of guaiacol on Pt/TiO₂: The modulation on guaiacol adsorption and H spillover

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